steam-set printing ink



Reissued June 26, 1951 STEAM-SET PRINTING INK Alfred F. Schmutzler,Teaneck, N. J., and Donald F. Othmer, Coudersport, Pa.

N Drawing.

Original No. 2,482,879, dated September 2'7, 1949, Serial No. 569,716,October 2'7,

1950, Serial No. 186,324

Matter enclosed in heavy brackets appears in the original patent butforms no part of this reissue specification; matter printed in italicsindicates the additions made by reissue.

21 Claims.

This invention relates to printing inks, and more particularly toprinting inks which harden by exposure to steam.

Printing inks which harden by the application of moisturein the form ofsteam or water, consist of compositions made from a water-miscibleliquid such as ethylene glycol, diethylene glycol or the like, in whichthere is dispersed a waterinsoluble binder such as Zein, a resin and acoloring material such as a pigment of the character of carbon black,chrome yellow, or the like, or a dyestuff. The hardening of the ink iscaused by exposing a printed film to steam or water. During the processof setting, the water-miscible liquid absorbs sufficient water to causethe precipitation of the binder and the pigment. Due to the nature ofthe process, it is necessary for he binder to be suificientlymoisture-sensitive so that the addition of water to the organic liquidcauses its separation, but the binder should have an adequate tolerancefor moisture so that it will not prematurely precipitate.

' Usually inks made with zein are too sensitive to high humidities, suchas about 50%, resulting in a breakdown on the printing press, withconsequent failure of proper distribution on the rollers and theresultant failure of the printing process.

Printing inks made by suspending coloring materials in a colloidaldispersion of from to 35% of soybean proteins, said proteins containingfrom 95% upwards of pure protein dispersion in diethylene glycol, using6% of guanidine carbonate as the dispersing agent, and made up to anapparent viscosity of 10 to poises as described by Schmutzler andOthmer, Industrial and Engineering Chemistry, 1196-1202 (1943), have atolerance for moisture and therefore, as contrasted with zein proteininks, do not break down on the press at high humidities andsatisfactorily harden if their printed films are exposed to steam. Theymay be used where water resistance of the printed film is not a factorof paramount importance. This soybean-protein diethylene glycoldispersion can be used with high oil absorption pigments, such as carbonblack, benzidene yellow, Prussian blue and the like.

Printing inks prepared from colloidal dispersions of other vegetableproteins such as alkaline extracted corn proteins, cottonseed globulin,hempseed globulin or the like, made up as the soybean protein ink abovedescribed to similar concentrations in diethylene glycol with acorresponding amount of peptizing agent, resemble the soybean proteininks in characteristics and performanc Application for reissue September22,

4 Printing inks made from dispersions of casein and other proteins ofanimal origin such as blood albumin, gelatin or the like, in polyhydricalcohols set to harder films than those made from soybean protein. Whenthe protein dispersions are made up to viscosities higher than 30poises, they are found to possess greater binding characteristics thanthe lower viscosity dispersions. It is also to be noted that printinginks made of the foregoing materials are usually alkaline in character.The alkalinity of the dispersions is a disadvantage as it sometimescauses a change in the hue of the'coloring materials and sometimeseifects the light-fastness thereof.

If the high viscosity dispersions are acidified, there is a decrease inthe water absorption of the dry ink films. I

All colloidal dispersions of these proteins, as contrasted with zein,may be blended with resins resulting in improved consistency of the inkas well as improved resistance of the printed film. In blends withresins, the protein dispersions usually impart hardness and moisturetolerance to the printing inks and sometimes plastic flow. Resinousmaterials such as long polymerized phenol modified indene coumaroneresin, a complex phenolic compound of the group comprising partiallypolymerized phenol modified indene coumarone resins, alkyd resins, ureaformaldehyde resins, rosin or the like, may be used for such purposes. I

If neutralized or slightly acid dispersions are to be used instead ofthe alkaline dispersions, it is advantageous to effect theneutralization or slight acidification of the alkaline peptizing agentsby the use of acids of higher molecular Weight than acetic acid orpropionic acid. We have found that maleic anhydride, phthalic anhydride,abietic maleic or fumaric acid modified rosin, linseed oil fatty-acid,acidic compounds as obtained by reacting the equivalent of one molecularweight of a dibasic acid With the equivalent of one molecular weight ofa dihydric alcohol or the like, may be used for acidifying purposes. Wehave also found that the alkaline dispersions may be neutralized by theaction of phenol, cresol, other phenols, phenol alcohols, phenylisothiocyanate or the like. The polyhydric alcohols of the dispersionswhen reacted with dibasic acids such as maleic acid or its anhydride,fumaric acid or the like, form soft resins which have a tendency toharden b oxidation. The alkyd resins as well as the proteins possess ahigh tolerance for moisture, and in case of printing inks made therefromthe contribution of the 3 proteins in the composition resides in anincreasing hardness. In other compositions such as employing rosin,diethylene glycol soluble pure phenol formaldehyde resins, andtricarboxylic acids obtained from diene modified rosin esters,

the proteins do contribute hardness as Well as water tolerance to thecomposition, whilst the resinous materials decrease the water absorptionof the ink films.

Accordingly it is among, the objects of thisinvention to provide proteindispersions which may be used for preparing printing inks having a greattolerance for moisture".

Another object of this invention is to provide printing inks which willset to hard, water resistant films when the printed films are exposed tomoisture.

Another object of this invention is to provide for the economicalproduction of dispersions which may be used for preparing printing inks.

The foregoing andother objects may be accom plished by using dispersionsof which the follow.- ing, are illustrative embodiments:

Example I- Parts Soybeans proteinscontaining. from 95% up..-

'wards of 'pure protein Guanidine carbonate 3 Dicyandiamide 3 Diethyleneglycol. '74

are heated while stirring to 125 130 o. in about 15. mini1tes, held atthis temperature for about 2 hours, then carefully the temperature israised r0140? C. in about 15 minutes, and held to l40 14'5.C. to anapparent viscosity, at room temperature, of about 200 poises (about.minutes to l. hour).

The resulting dispersion is mixed and milled with a coloring material,such as. 25 parts car-.- bon black;

" Example II The dispersion, as prepared, in Examplel, is neutralized.with" glacial acetic acidlabout 4 parts). After cooling, it. is'niixed'and with parts Prussian, blue.

ExampleIII Pa s Soybean proteins containing from 95% upwards of pureprotein 20 Ethylene 'dia'mine a Diethylene glycol 76 are heated whilestirring to 130C. in about. 20 minutes'and held between Bil-1355 C. toaviscosity at room temperature. of about 300 poises (about 1 to. 2hours), then, at 130135, C. This vehicle is mixed and milled withloo-parts ch dm yellow.

' Example IV The dispersion, as prepared in Example III, is neutralizedwith glacial acetic acid (about 4 parts). After cooling, it is mixedand. milled with 35 parts Prussian blue.

' ExampleV Parts Casein 20 Guanidine. carbonate 2' Diethylene glycol 78are heated, while stirring, for 3. hours at 80? C. Toward the endof'thistime, 2,.parts acetic an; hydride are added, drop. by drop.Aftercooling, 25. parts carbon black are mixed with the dispersion, andthe mixture is passed over a threeroller ink mill.

Example VI Parts Casein 20 Guanidine, carbonate 3 Diethylene glycol '7'?are heated, while stirring, for hour at C. Toward the end of this time,10 parts phthalic anhydride are added, and the temperature is raised to-140" C. in about ten minutes and held there for. one hour. Aftercooling, it is mixedand milled with 30 parts lithol red.

Example VII N Parts Acid casein 30 Guanidine carbonate 3 Diethyleneglycol 67 areheated at 110 and stirred at this tempera; ture for 1 hour,then, 16 parts phthalic anhydride are added gradually, and afteradditionthefdispersion is heated at 110-420" C. for'anadditional hour.The vehicle is mixed and milled into an ink with 30 parts carbon black.

Example VIII Parts 20% soybean protein dispersion containing from 95%upwards of pure protein as pre-' pared in Example I Q 100 Adiethylene-glycol soluble, partially poly} merized indene 20 are heatedat C. for 30 minutes, then. 10 parts phthalic acid anhydride are addedand the mixture is reacted for 1 hour. The resulting dis.- persion ismixed and milled into an ink with i Diethylene glycol 5 20 Carbon blacks ;A5} 40 Example IX P l??? Soybean protein having from 95% upwardsorpure protein content 1 20 Methylamine (crude) V Diethylene glycol V areheated, while stirring, to.1'25-l30". C- inabout 15 minutes, held atthis temperature-for a out l hour, then carefully the temperature, is rato '130" c. in about 10 minutes and held at this eng perature for 2hours. Atthe end ofthisreaction period Bans Maleic anhydride A softphenolic-modif ed inde e-stamens I resin 1 10 are added toward the endof this period. There.- sulting dispersion is mixed with G'Oparts litholredand passed over a three-roller ink mill.

m le Soybean protein having from 95%npwardsof pure protein content 30Ethylene diamine 2 Ethylene glycol 68 are heated while stirring at 140C. for 1 hour, then Rosin T Phthalic anhydride are added and the mixtureis continued to be heated at 140 C. for 3 hours,

are mixed with this dispersion and the mixture is milled into an ink.

Example X1 100 parts of 20% soybean protein dispersion containing from95% upwards of pure protein, as prepared in Example III 5 partsdiethylene glycol soluble pure phenolformaldehyde resin, dissolved. in

parts triethylene glycol are heated at 140 C. for 20 minutes, then 30parts of phthalic anhydride are added and the mixture is heated for 1hour at 130-140" C. This dispersion is mixed and milled into an ink withParts Diethylene glycol 30 Chrome yellow 200 Example XII Parts Soybeanprotein having from. 95% upwards of pure protein content 30 Ethylenediamine 2 I Ethylene glycol 68 are mixed well, and heated to 135 C. in30 minutes and kept between 135-145" C. while stirring and adding PartsR0sin- 10 Phthalic anhydride 90 and the mixture is held between 135-145C. for 2 hours. Then. it is diluted with 60 parts diethylene glycol. Theresulting vehicle is mixed and milled with 100 parts lithol red.

Example IHII Parts Soybean having from 95% upwards of pure proteincontent 30 Guanidine carbonate 3 Ethylene glycol 6'7 heated to 125 C. in/2 hour, held at 120-130 C. for 2 hours, then Parts Phthalic acidanhydride 84 Rosin 8 are added and heated for 1 hour between 130-140 C.While cooling, below 110 C., the viscous vehicle is thinned with partsdiethylene glycol. The vehicle is mixed and milled with 300 parts ofchrome yellow.

Example XIV Parts Casein 40 Ethylene diamine 6 Ethylene glycol 54 6Example XV Parts Casein 30 Ethylene diamine 2 Ethylene glycol 68 areheated to 110 C. in about 30 minutes, at 110 0., add,

- Parts Rosin G 10 Phthalic anhydride 90 and heat for 2 hours at 135-145C. then add, 6-0 parts diethylene glycol and cool. The vehicle is mixedwith 85 parts lithol red and the mixture is milled on a three-roller inkmill.

We have found that glycerol and glycols other than those heretoforedescribed may be used in preparing the dispersions. Among these glycolsare propylene glycol-dipropylene and tetraethylene glycol. The variousglycols of the olefines described herein may be designated as alkyleneglycols.

Pigments and. coloring materials either of organic or inorganiccharacter which impart coloring to the dispersions rendering them usefulas printing ink, may be designated as pigments.

We have found that other efiective peptizing agents, in addition tothose heretofore described, for dispersing the proteins are thefollowing nitrogenous compounds: dimethylamine, diethylamine,diethylaminoethanol, n-butylaminefdibutylamine, propylene diamine,diethylene tri amine, dipropylene triamine, triethylene tetraamine,ammonia (aqueous solution) and aldehyde ammonia. We have also found thatdispersions of the proteins may be prepared by using other compounds forthe peptization. These are: ammonium bicarbonate, ammonium chloride,ammonium nitrate, ammonium thiocyanate, phthalic anhydride, maleicanhydride, acetic acid, ammonium sulfate, ammonium oxalate, aniline,phenol, nitroethane, nitropropane, nitrobenzene, calcium hydroxide,urea, thiourea and 2-nitro- 2-methyl-1,3-propanediol. The foregoingcompounds and those heretofore described in the examples may bedesignated as peptizing agents.

Having described our invention, we claim:

1. A dispersion consisting of a soybean protein containing from 95%upwards of pure protein, a polyhydric alcohol selected from the groupconsisting of ethylene glycol and diethylene glycol, and a proteinpeptizing agent, said peptizing agent being guanidine carbonate.

2. A dispersion consisting of a soybean protein containing from 95%upwards of pure protein, diethylene glycol, a peptizing agent, thepeptizing agent being guanidine carbonate, and a pigment.

3. A dispersion consisting of a soybean protein containing from. 95%upwards of pure protein, dispersed in a polyhydric alcohol, a resin, apeptizing agent and a pigment: wherein the polyhydric alcohol isselected from the group consisting of ethylene glycol and diethyleneglycol, the peptizing agent being guanidine carbonate.

4. A printing ink essentially consisting of a dispersion of soybeanprotein containing from 95% upwards of pure protein in diethyleneglycol, the

said protein being peptized by the actionof guanidine carbonate; a resinand a pigment.

5. A printing ink essentially consisting of a dispersion of a soybeanprotein having from upwards of pure protein in diethylene glycol, thesaid protein being peptized by the action of guanidine carbonate, and apigment.

iia'sse 7 6. A dispersion consisting of a soybean protein containingfrom 95% upwards of pure protein, ethylene glycol, a peptizi-ng agent,the peptiaihg agent being guanidine carbonate, and a pigment. 'l. Aprinting i-nk essential-1y consisting of a dispersion of soybean proteincontaining from 95% upwards of pure protein in ethylene glycol, the saidprotein being peptized by the action of guanidine carbonate; a resin anda pigment,

8. A printing ink essentially consisting of a dispersion of a soybeanprotein having from 95% upwards of pure protein in ethylene glycol, the

said protein being peptired by the action of guanidine carbonate, and apigment.

9. A printing ink vehicle consisting essentially of a dispersion of abinder, a protein peptieing agent and a substantially anhydroushygroscopic liquid, said binder consisting essentially of a dry,substantially anhydrous, non-prolamine protein having high watertolerance and being dispersible in nitrogen base material, said proteinbeing dispersed by the action of said peptieing agent,

said liquid consisting essentially of a polyhydric alcohol having 2-3hydroxy groups and 2-8 carbon atoms, said printing ink vehicle having ahigh humidity and water tolerance and being readily settable on exposureto steam.

'10. A printing ink vehicle consisting essentially of a dispersion of abinder, a protein peptizing agent and a substantially anhydroushygroscopic liquid, said binder consisting essentially of a dry,substantially anhydrous non-prolamine protein having high water.tolerance and being dispersible in nitrogen base material, said proteinbeing dispersed by the action of the protein peptieing agent, saidpeptizing agent being a nitrogen containing compound and said liquidconsisting essentially of a polyhydric alcohol having from 2 to 3hydroxy groups and 2 to 8 carbon atoms, said printing ink vehicle havinga high humidity and water tolerance and being readily settable onexposure to steam.

11. A printing ink vehicle consisting essentially of a dispersion of abinder, a protein pepti'zing agent and a substantially anhydroushygroscopic liquid, said binder consisting essentially of a dry,substantially anhydrous non-prolamine protein, having high watertolerance and being dispersible in nitrogen base material, said proteinbeing dispersed by the action of the protein peptizing agent, saidpeptieing agent being a basic soluble amino compound and said liquidconsisting essentially of a polyhydric alcohol having from 2 to 3hydrozcy groups and 2 to 8 carbon atoms, said printing ink vehiclehaving a high humidity and water tolerance and being readily settable onexposure to steam.

12. A printing ink vehicle consisting essentially of a dispersion of abinder, a protein peptieing agent and a substantially anhydroushygroscopic liquid, said binder consisting essentially of a dry,substantially anhydrous soybean protein dispersed by the action of theprotein peptizing agent, said peptieing agent being a nitrogencontaining compound and said liquid consisting esagent. and asubstantially anhydrous hygroscopic liquid, said binder consistingessentially of a dry, substantially anhydrous 'non-prolamine proteinhaving high water tolerance and being 'dis'pers ible in nitrogen basematerial, said protein being dispersed by the action of the proteinpeptieing agent, and said liquid consisting essentially of a polyhydricalcohol selected from the group or diethylene glycol and ethyleneglycol, said printing ink vehicle having a high humidity and watertolerance and being readily settable on exposure to steam.

14. A printing ink vehicle consisting of a dispersion of a binder, aprotein peptizing agent, and a substantially anhydrous hygroscopicliquid, said binder consisting essentially of a dry, substantiallyanhydrous non-prolamine protein having high water tolerance and bein'gdispersible in nitrogen base material, said protein being dispersed bythe action of the protein peptie ing agent, said pe'p'tieing agent beinga basic soluble amino compound, and said liquid consisting essentiallyof a polyhydric alcohol selected from the group of diethylene glycol andethylene glycol, said printing ink vehicle having a high humidity andtuater tolerance and being readil settable on exposure to steam.

15. A printing ink vehicle consisting essentially of a dispersion oj'abinder, a protein peptizing agent and a substantially anhydroushygroscopic liquid, said binder consisting essentially of a dry,substantially anhydrous non-prolamine protein having high watertolerance and being dispersible in nitrogen base material, said proteinbeing dispersed by the action of the protein peptieing agent, saidpeptizing agent being a nitrogen containing compound, and said liquidconsisting essentially of a polyhydric alcohol selected from the groupof diethylene glycol and ethylene glycol, said printing ink vehiclehaving a high humidity and water tolerance and being readily settable onexposure to steam.

16. A printing ink consisting of coloring matter in a dispersion of aresin binder, a protein binder, a pr'otein peptieing agent and asubstantially anhydrous hygroscopic liquid, said binder consistingessentially of a dry, substantially anhydrous non-prolamine proteinhaving high wa ter tolerance and being dispersible in nitrogen basematerial, said protein being dispersed by the action of the proteinpeptieing agent, and said liquid consisting essentially of a polyhydricalcohol having from 2 to 3 hydromy groups and 2 to 8 carbon atoms,saidprinting ink having a high humidity and water tolerance and beingreadily settable on exposure to steam.

1?. A printing ink consisting of coloring matter in a dispersion of aresin binder, a protein binder, a protein peptieing agent and asubstantially anhydrous hygroscopic liquid, said binder consistingessentially of a dry, substantially anhydrous, non-prolamine proteinhaving'highwater tolerance and being dispersibl'e in nitrogen basematerial, said protein being dispersed by the action 0 the proteinpeptizing agent, said peptieingfiagent being a basic soluble aminocompound,

ter in a dispersion of a resin binder, a protein binder, a proteinpeptizing agent and a substantially anhydrous hygroscopic liquid, saidbinder consisting essentially of a dry, substantially anhydrousnon-prolamine protein having high water tolerance and being dispersiblein nitrogen base material, said protein being dispersed by the action ofa protein peptizing agent, said peptieing agent being a nitrogencontaining compound and said liquid consisting essentially of apolyhydric alcohol having from 2 to 3 hydromy groups and 2 to 8 carbonatoms, said printing ink haoing a high humidity and water tolerance andbeing readily settable on exposure to steam.

19. A printing ink consisting of coloring matter in a dispersion of aresin binder, a protein binder, a protein peptizing agent and asubstantially anhydrous hygroscopic liquid, said binder consistingessentially ofa dry, substantially anhydrous non-prolamine proteinhaving high wa ter tolerance and being dispersible in nitrogen basematerial, said protein being dispersed by the action of theproteinpeptizing agent, said peptizing agent being (a nitrogen containingcompound, and said liquid consisting essentially of a polyhydric alcoholselected from the group consisting of ethylene glycol and diethyleneglycol, said printing ink having a high humidity and wa ter toleranceand being readily settable on ea:- posure to steam.

20. A printing ink consisting of coloring matter in a dispersion of aresin binder, a protein binder, a protein peptizing agent and asubstantially anhydrous hygroscopic liquid, said binder consistingessentially of a dry, substantially anhydrous non-prolamine proteinhaving high water tolerance and being dispersible in nitrogen basematerial, said protein being dispersed by the action of the proteinpeptizing agent, and said liquid consisting essentially of a polyhydricalcohol selected from the group of diethylene glycol and ethyleneglycol, said printing ink having a high humidity and water tolerance andbeing readily settable on exposure to steam.

21. A printing ink consisting of coloring matter in a dispersion of aresin binder, a protein binder, a protein peptizing agent and a substantially anhydrous hygroscopic liquid, said binder consisting essentiallyof a dry, substantially anhydrous nomprolamine protein having high watertolerance and being dispersible in nitrogen base material, said proteinbeing dispersed by the action'of the protein peptizing agent, saidpeptizing agent being a basic soluble amino compound, and said liquidconsisting essentially of a polyhydric alcohol selected from the groupof diethylene glycol and ethylene glycol, said printing ink having ahigh humidity and water tolerance and being readily settable on exposureto steam.

ALFRED F. SCHMUTZLER.

DONALD F. O'IHMIER.

REFERENCES CITED The following references are of record in the file ofthis patent or the original patent:

UNITED STATES PATENTS Number Name Date 1,962,823 Kurz et al. June 12,1934 2,185,110 Coleman Dec. 26, 1939 2,198,596 Atwood Apr. 30, 19402,292,624 Fawthrop Aug. 11, 1942 2,298,269 Atwood Oct. 13, 19422,309,380 Brother Jan. 26, 1943 2,324,105 Nadeau July 13, 1943 2,335,882Pingarron Dec. 7, 1943 FOREIGN PATENTS Number Country Date 20,249Australia Aug. 29, 1935 of 1934 OTHER REFERENCES Industrial andEngineering Chemistry, Nov. 1943, pages 1196 to 1202.

